Absolute Orientation of Molecules with Competing Hydrophilic Head Groups at the Air/Water Interface Probed with Sum Frequency Generation Vibrational Spectroscopy

和频振动光谱(SFG-VS)研究中由基团在界面上取向所引起的光谱增强或相消的干涉现象为研究分子在界面上的绝对取向提供了一种直接的测量方法. 这一方法比SFG实验中复杂的相位测量方法更为直接和简单可行. 以在空气/水界面取向已知的对羟基苯腈(PCP)分子的氰基(-CN)基团为相位参考来获得3,5-二甲基对羟基苯腈(35DMHBN)和2,6-二甲基对羟基苯腈(26DMHBN)分子在空气/水界面的取向信息. 通过对这三种分子的水溶液和它们两两混合溶液界面上-CN基团和频振动光谱强度的比较,发现在空气/水界面的3     

Vibrational Spectra and Adsorption of Trisiloxane Superspreading Surfactant at Air/Water Interface Studied with Sum Frequency Generation Vibrational Spectroscopy

使用界面和频振动光谱(SFG-VS)测量了空气/水界面三甲基硅烷表面活性剂Silwet L-77的C-H伸缩振动光谱．这些光谱峰主要是在2905 cm-1附近属于-Si-CH3基团的对称伸缩(SS)振动,在2957 cm-1的主要是-Si-CH3基团反对称伸缩(AS)振动,以及明显较弱的在2880 cm-1附近的属于-O-CH2-基团的对称伸缩(SS)振动．通过比较低于和高于临界聚集或胶束浓度(CAC)的SFG-VS偏振光谱显示Silwet L-77分子的C-H基团取向在不同的界面密度下变化很小．SFG-VS测量的吸附等温线表明Silwet L-77分子在空气/水界面没有形成所谓的双层结构的迹象．Silwet L-77分子在空气/水界面的Gibbs吸附自由能为-42.2±0.8 kJ/mol,表明该分子具有很强的表面吸附能力．     

高速摄影在流体动力学不稳定性研究中的应用

用高速摄影技术研究了高压气体膨胀驱动空气-水界面的瑞利-泰勒不稳定性,获得了空气-水界面的不稳定性清晰图像,得到气炮尖顶运动速度及湍流混合层高度增长速度与时间关系曲线。在横式激波管上用高速纹影诊断技术研究了激波作用空气-SF6界面的里克特迈耶-梅什科夫不稳定性,初步获得了实验图像,可清晰显示混合区变化过程。     

Simulation Study on the Structure and Dynamics of Water in Sodium Tetrafluoroborate/Water

应用分子动力学模拟方法研究了室温条件下四氟硼酸钠(NaBF₄)/水混合体系中水分子的微观结构、IR光谱以及转动动力学. 考察了混合物体系中水分子的摩尔分数浓度分别为6.25%、25.0%、50.0%、75.0%、90.0% 和99.6%时体系的结构和动力学性质. 研究显示在不同水分子含量的混合物中水分子以自由分子存在,随着混合物中水分子摩尔分数的增加,水分子的转动和弯曲振动带红移,而O-H伸缩振动蓝移,混合物中水分子内和分子间的氢键和非谐性相互作用增强,分子平动和转动变得困难和缓慢,研究结果与实验观测一致.     

液体水中O-H 弯曲振动能量弛豫的数值

应用分子动力学模拟方法研究了液相水中水分子O-H弯曲振动能量弛豫的机理. 采用刚性和柔性溶剂模型来探讨振动能量弛豫的不同通道. 研究发现，刚性溶剂中O?H弯曲振动泛频的弛豫时间为174 fs而柔性溶剂中为115 fs. O-H 弯曲振动泛频振动能量弛豫的主要途径是跃迁O?H 弯曲振动基频. O-H弯曲振动基频的弛豫时间为204 fs，与实验值170 fs符合得较好.     

蜡晶对油水界面稳定性的耗散粒子动力学研究

随着油田的不断开发，石蜡结晶和油水乳化作用为含蜡原油的开采、运输和储存带来巨大挑战。本文采用耗散粒子动力学方法研究了石蜡相变结晶对油水界面稳定性的影响。首先，计算了石蜡分子的序参量，揭示了水分子和油分子均会促进石蜡分子形成有序的固态晶体结构。其次，发现随着蜡含量的增加，油–水界面的表面张力逐步提高，石蜡分子会提高油–水界面的稳定性。最后，得到油–水界、蜡–水界面，蜡–油界面表面张力随温度的变化关系(298～348 K)。结果表明，当温度低于308 K，油–水界面和蜡水界面都能维持其界面的稳定性。对于蜡–油界面，当温度高于308 K时，达到石蜡的析蜡温度，石蜡晶体逐步熔化，蜡–油之间的界面张力急剧减小，蜡油界面逐渐消失。     

全内反射构型下分子在十六烷-水界面取向角度的二次谐波测量

测量了在全内反射条件及非全内反射条件下,两种探针分子在十六烷-水界面上的取向角度.通过详细的偏振分析,发现探针分子在两种构型下的取向角度测量结果一致.表明全内反射条件下,取向角度的测量和偏振分析同样是准确且可行的.     

十二烷基苯磺酸钠在癸烷-水界面吸附的MD模拟

本文采用分子动力学方法研究了具有十二烷基苯磺酸钠(SDBS)吸附的癸烷-水界面的微观特性,从浓度分布和分子构象出发,分析界面分子排布对癸烷-水界面微观结构和性质的影响。模拟结果表明癸烷水界面厚度约为0.378nm,界面处水分子偶极矩方向和癸烷分子倾向于与界面平行;SDBS在界面的吸附使得界面厚度增大,油水相互作用减弱,扰乱了水和癸烷分子在界面的定向排列;同时,发现癸烷水界面存在空隙,结合亲水基强烈的静电作用,使得界面处水分子扩散加剧,界面变形能力增强。     

低温下冰的拉曼光谱研究

采用变温装置,在-30℃至-190℃温度范围内我们对冰行进了原位低温拉曼光谱测量.并利用光谱分析软件对冰的拉曼光谱带行进了分析,得到O-H键振动的三个拉曼峰随温度的变化规律.应用氢键理论对实验结果进行了分析,结果表明O-H键的ν3(E g)反对称伸缩振动和ν1(B 1g)不同向对称伸缩振动受氢键影响较大,并且ν3(E g)的拉曼峰位与温度成很好的线性关系有潜在的应用价值.     

空气/甲醇界面和频振动光谱的定量偏振分析

对空气／甲醇液体界面的和频振动光谱进行了定量的理论分析．虽然甲醇的红外和Raman光谱中都具有明显的反对称伸缩振动峰,但该光谱峰在界面和频振动光谱中却从未被观测到．利用已知的甲醇液体的红外和Raman光谱对和频振动光谱的键极化模型进行了修正,从而对此实验现象进行了定量的解释．此修正可以广泛地应用于界面和频振动光谱的研究中．     

Impact of intermolecular vibrational coupling effects on the sum-frequency generation spectra of the water/air interface

ABSTRACT

We have examined the impact of intermolecular vibrational coupling effects of the O-H stretch modes, as obtained by the surface-specific velocity-velocity correlation function approach, on the simulated sum-frequency generation spectra of the water/air interface. Our study shows that the inclusion of intermolecular coupling effects within the first three water layers, i.e. from the water/air interface up to a distance of 6?Å towards the bulk, is essential to reproduce the experimental SFG spectra. In particular, we find that these intermolecular vibrational contributions to the SFG spectra of the water/air interface are dominated by the coupling between the SFG active interfacial and SFG inactive bulk water molecules. Moreover, we find that most of the intermolecular vibrational contributions to the spectra originate from the coupling between double-donor water molecules only, whereas the remaining contributions originate mainly from the coupling between single-donor and double-donor water molecules.     

Motional effect in surface sum-frequency vibrational spectroscopy

Fast orientational motion of molecules at a surface can affect the sum-frequency vibrational spectra of the surface. Calculation shows that the effect is significant if the molecular orientation varies over a broad range within the vibrational relaxation time. The stretch vibration of the free OH bonds at the vapor/water interface is used to illustrate the importance of the effect.     

Ultrafast reorientation of dangling OH groups at the air-water interface using femtosecond vibrational spectroscopy

We report the real-time measurement of the ultrafast reorientational motion of water molecules at the water-air interface, using femtosecond time- and polarization-resolved vibrational sum-frequency spectroscopy. Vibrational excitation of dangling OH bonds along a specific polarization axis induces a transient anisotropy that decays due to the reorientation of vibrationally excited OH groups. The reorientation of interfacial water is shown to occur on subpicosecond time scales, several times faster than in the bulk, which can be attributed to the lower degree of hydrogen bond coordination at the interface. Molecular dynamics simulations of interfacial water dynamics are in quantitative agreement with experimental observations and show that, unlike in bulk, the interfacial reorientation occurs in a largely diffusive manner.     

Ultrafast vibrational energy transfer between surface and bulk water at the air-water interface

We report a femtosecond time-resolved study of water at the neat water-air interface. The O-H stretch vibrational lifetime of hydrogen-bonded interfacial water is measured using surface-specific 4th-order nonlinear optical spectroscopy with femtosecond infrared pulses. The vibrational lifetime in the frequency range of 3200 to 3500 cm(-1) is found to closely resemble that of bulk water, indicating ultrafast exchange of vibrational energy between surface water molecules and those in the bulk.     

Molecular structure of polystyrene at Air/Polymer and Solid/Polymer interfaces

IR-visible sum-frequency generation (SFG) spectroscopy has been used in a total internal reflection geometry to study the molecular structure of polystyrene (PS) at PS/sapphire and PS/air interfaces, simultaneously. The symmetric vibrational modes of the phenyl rings dominate the SFG spectra at the PS/air interface as compared to the antisymmetric vibrational modes at the PS/sapphire interface. This indicates approximately parallel orientation of the phenyl rings at the PS/air interface while nearly perpendicular orientation at the PS/sapphire interface, with respect to the surface normal.     

Structure and dynamics of water at liquid–vapour interfaces covered by surfactant monolayers of neutral stearic acid and charged stearate ions

The behaviour of water molecules at liquid–vapour interfaces with a surfactant monolayer of either stearic acid molecules or anionic stearate ions is investigated by means of molecular dynamics simulations. The density and dipolar orientational profiles and also the dynamics of translational and rotational motion of interfacial water molecules are calculated in the present work and the results are compared with the bulk liquid water and also of liquid–vapour interface of surfactant-free water. The present simulation results are also compared with available experimental results of similar interfacial systems with a monolayer of either neutral or ionic surfactants.     

羟基对界面水分子的扰动与其对非离子型氢氟烃杂化表面活性剂聚集行为的改变

本文合成并比较了具有和不具有羟基的两种非离子型氢氟烃杂化表面活性剂,它们均表现出良好的热稳定性和优异的表面活性. 实验观察到羟基对改变其溶液的表面张力和所形成胶束的形态具有较大的影响. 该作用可归因于烷烃基团从空气/水表面上方到其下方的重排以及由羟基诱导的界面水结构的扰动. 本工作提供了一种通过修改界面处的取向结构来弱化碳氢链和碳氟链之间的不混溶性,从而利于设计具有不同界面性质表面活性剂的策略.     

Interfacial Free Energy at the Metallic Crystal–Melt Interface

The technique for estimating the interfacial free energy of transition-metal nanocrystals and its anisotropy at the interface with their melts has been developed. The expression for the coordinate of the Gibbs’ interface, which takes into account the size dependence, has been derived. The interfacial free energy of crystal faces at the interface with the related melts of monomorphic 4d and 5d metals decreases nonlinearly with a decrease in the nanocrystal size and, at a certain size, disappears. At the nanocrystal radius of more than 10 nm, the interfacial free energy of the faces approaches that for a macrocrystal. The temperature dependence of the interfacial free energy at the crystal–melt interface is almost linear. The technique developed is shown to be in agreement with the known experimental data for mono- and polycrystals and applicable for estimating the orientational, temperature, and size dependences of the interfacial free energy at the interfaces of nano-, micro-, and macrocrystals with their melts.     

Influence of intramolecular vibrations in charge redistribution at the pentacene-graphite interface

We have investigated the relation between the intramolecular vibrational modes of pentacene and the charge redistribution at the pentacene-graphite interface by using high-resolution electron-energy-loss-spectroscopy. The three main vibrational peaks shift to lower energies as the pentacene film thickness decreases. In order to discuss this energy shift, we have calculated the vibrational energies of a free pentacene molecule by changing its charge state. We have also calculated the vibrational energies of a pentacene molecule adsorbed on a graphite sheet by changing the pentacene-graphite distance. Taking the experimental and calculation results into account, we conclude that the observed energy shifts result from an intramolecular charge redistribution. The present results indicate that the effect of an intramolecular charge redistribution is essential to discuss the origin of an energy shift observed in a vibrational study of an organic molecule/substrate interface.